Method for Preparation of a Nanocomposite Material by Vapour Phase Chemical Deposition

Abstract

The invention relates to a method for preparing a nanocomposite material by simultaneous vapour phase chemical deposition and vacuum injection of nanoparticles and to the materials and nanoparticles obtained thus and the application thereof.

1 . A method of forming a nanocomposite, consisting of at least two elements, on the surface of a substrate, said method comprising at least one chemical vapor deposition step in the presence of a gas, characterized in that said step is carried out by simultaneous direct liquid injection:
 a) of at least one injection liquid I 1  consisting of:
 i) at least one liquid precursor of one of said elements or 
 ii) a solution of at least one precursor of one of said elements in an organic solvent; and 
   b) of solid nanoparticles of the other element, said nanoparticles being present in the form of a homogeneous dispersion within the injection liquid I 1  and/or within an injection liquid I 2  separate from the injection liquid I 1 .   
   
   
       2 . The method as claimed in  claim 1 , characterized in that the liquid precursors or precursors dissolved in an organic solvent are selected from the group consisting of organometallic precursors and metal salts. 
   
   
       3 . The method as claimed in  claim 2 , characterized in that said metal salts are selected from the group consisting of chlorinated metal salts and ammonium metal salts. 
   
   
       4 . The method as claimed in  claim 2 , characterized in that the organometallic precursors are selected from the group consisting of metal dialkyls, metal β-diketonates, precursors with carbonyl or phosphine ligands or with chlorinated ligands, n-cyclopentadienyl metal complexes, cyclooctadienyl metal complexes and precursors with an olefin or allyl group. 
   
   
       5 . The method as claimed in  claim 4 , characterized in that said metals are chosen from the metals of the first three rows of columns IVB to IB of the Periodic Table, Li, Si, Ge and alloys thereof. 
   
   
       6 . The method as claimed in  claim 1 , characterized in that the organometallic precursors are selected from the group consisting of titanium tetraisopropoxide and platinum acetylacetate. 
   
   
       7 . The method as claimed in  claim 1 , characterized in that the organic solvent for the injection liquid I 1  comprises a solvent having an evaporation temperature below the decomposition temperature of the precursor(s). 
   
   
       8 . The method as claimed in  claim 7 , characterized in that said solvent comprises a liquid organic compounds having an evaporation temperature between 50 and 200° C. inclusive under normal pressure conditions. 
   
   
       9 . The method as claimed in  claim 7 , characterized in that said solvent is selected from the group consisting of mesitylene, cyclohexane, xylene, toluene, n-octane, acetylacetone, ethanol and mixtures thereof. 
   
   
       10 . The method as claimed  claim 1 , characterized in that the injection liquid I 1  further comprises an amine and/or a nitrile and/or water. 
   
   
       11 . The method as claimed in  claim 10 , characterized in that the total amount of amine and/or nitrile and/or water in the injection liquid I 1  is less than 20% by volume. 
   
   
       12 . The method as claimed in  claim 10 , characterized in that the amine is selected from the group consisting of from n-hexylamine, isobutylamine, di-sec-butylamine, triethylamine, benzylamine, ethanolamine, diisopropylamine, polyamines and mixtures thereof. 
   
   
       13 . The method as claimed in  claim 10 , characterized in that the nitrile is selected from the group consisting of from acetonitrile, valeronitrile, benzonitrile, propionitrile and mixtures thereof. 
   
   
       14 . The method as claimed in  claim 1 , characterized in that the solid nanoparticles present in the form of a dispersion within the injection liquids I 1  and/or I 2  are chosen from mineral nanoparticles. 
   
   
       15 . The method as claimed in  claim 14 , characterized in that the mineral nanoparticles are selected from the group consisting of from silica oxide, titanium oxide, zirconium oxide and cerium oxide nanoparticles. 
   
   
       16 . The method as claimed in  claim 1 , characterized in that the nanoparticles are carbides or nitrides. 
   
   
       17 . The method as claimed in  claim 1  characterized in that the injection liquid I 2  comprises a solvent having an evaporation temperature below the decomposition temperature of the precursor(s). 
   
   
       18 . The method as claimed in  claim 1 , characterized in that the injection liquid or liquids (I 1  and I 2 ) are introduced into a vaporization device via which they are sent into a heated deposition chamber that contains the substrate, at least one surface of which has to be coated with said nanocomposite. 
   
   
       19 . The method as claimed in  claim 1 , characterized in that the deposition is carried out at a substrate temperature not exceeding 500° C. 
   
   
       20 . The method as claimed in  claim 1 , characterized in that the deposition is carried out at atmospheric pressure or under a vacuum with a pressure of 40 to 1000 Pa. 
   
   
       21 . The method as claimed in  claim 1 , characterized in that it is carried out with plasma assistance. 
   
   
       22 . The method as claimed in  claim 1 , characterized in that the substrate is dense or porous and is selected from the group consisting of from glass, silicon, metals, steels, ceramics, fabrics, zeolites and polymers. 
   
   
       23 . The method as claimed in  claim 1 , characterized in that the gas is composed of a reactive gas and/or a vapor-carrying inert gas. 
   
   
       24 . The method as claimed in  claim 23 , characterized in that the reactive gas is selected from the group consisting of from oxygen, hydrogen, ammonia, nitrous oxide, carbon dioxide, oxone, nitrogen dioxide and mixtures thereof. 
   
   
       25 . The method as claimed in  claim 23 , characterized in that the vapor-carrying inert gas is selected from the group consisting of from argon, nitrogen, helium and mixtures thereof. 
   
   
       26 . A supported nanocomposite that can be obtained by implementing the method as defined in  claim 1 , characterized in that it consists of:
 i) either a continuous layer consisting of a metal, oxide, carbide or nitride matrix having inclusions of at least one family of nanoparticles selected from the group consisting of from metal nanoparticles, oxide nanoparticles, carbide nanoparticles and nitride nanoparticles;   ii) or a discontinuous dispersion of nanoparticles, said dispersion being in the form of a juxtaposition of at least two families of nanoparticles selected from the group consisting of from metal nanoparticles, oxide nanoparticles, carbide nanoparticles and nitride nanoparticles.   
   
   
       27 . The composite as claimed in  claim 26 , characterized in that it consists of:
 i) a continuous oxide matrix having inclusions of at least one family of nanoparticles selected from the group consisting of from metal nanoparticles, carbide nanoparticles, nitride nanoparticles and oxide nanoparticles, the oxide of the latter being different from the oxide from which the continuous matrix is formed;   ii) a continuous matrix of a metal or a metal alloy having inclusions of at least one family of nanoparticles selected from the group consisting of from carbide nanoparticles, nitride nanoparticles, oxide nanoparticles and nanoparticles of a metal (or a metal alloy) of different nature from that of the metal or the metal alloy from which the continuous matrix is formed;   iii) a continuous matrix of a nitride having inclusions of at least one family of nanoparticles selected from the group consisting of from metal nanoparticles, carbide nanoparticles, oxide nanoparticles and nanoparticles of a nitride of different nature from the nitride from which the continuous matrix is formed; and   iv) a continuous matrix of a carbide having inclusions of at least one family of nanoparticles selected from the group consisting of from metal nanoparticles, oxide nanoparticles, nitride nanoparticles and nanoparticles of a carbide of different nature from the carbide from which the continuous matrix is formed.   
   
   
       28 . The composite as claimed in  claim 26 , characterized in that it comprises at least one oxide and at least one metal. 
   
   
       29 . The use of a nanocomposite as defined in  claim 26 , based on silver and titanium, as an antibacterial coating. 
   
   
       30 . The use of a nanocomposite as defined in  claim 26 , based on platinum and mineral nanoparticles, as an electrocatalyst.